Deep Mantle Conditions Research Articles

Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO2H at High Pressure.

The cycling of hydrogen plays an important role in the geochemical evolution of our planet. Under high-pressure conditions, asymmetric hydroxyl bonds tend to form a symmetric O-H-O configuration in which H is positioned at the center of two O atoms. The symmetrization of O-H bonds improves their thermal stability and as such, water-bearing minerals can be present deeper in the Earth's lower mantle. However, how exactly H is recycled from the deep mantle remains unclear. Here, we employ first-principles free-energy landscape sampling methods together with high pressure-high temperature experiments to reveal the dehydrogenation mechanism of a water-bearing mineral, FeO2H, at deep mantle conditions. Experimentally, we show that ∼50% H is released from symmetrically hydrogen-bonded ε-FeO2H upon transforming to a pyrite-type phase (Py-phase). By resolving the lowest-energy transition pathway from ε-FeO2H to the Py-phase, we demonstrate that half of the O-H bonds in the mineral rupture during the structural transition, leading toward the breakdown of symmetrized hydrogen bonds and eventual dehydrogenation. Our study sheds new light on the stability of symmetric hydrogen bonds during structural transitions and provides a dehydrogenation mechanism for hydrous minerals existing in the deep mantle.

Carbon-bearing silicate melt at deep mantle conditions

Knowledge about the incorporation and role of carbon in silicate magmas is crucial for our understanding of the deep mantle processes. CO2 bearing silicate melting and its relevance in the upper mantle regime have been extensively explored. Here we report first-principles molecular dynamics simulations of MgSiO3 melt containing carbon in three distinct oxidation states - CO2, CO, and C at conditions relevant for the whole mantle. Our results show that at low pressures up to 15 GPa, the carbon dioxide speciation is dominated by molecular form and carbonate ions. At higher pressures, the dominant species are silicon-polyhedral bound carbonates, tetrahedral coordination, and polymerized di-carbonates. Our results also indicate that CO2 component remains soluble in the melt at high pressures and the solution is nearly ideal. However, the elemental carbon and CO components show clustering of carbon atoms in the melt at high pressures, hinting towards possible exsolution of carbon from silicate melt at reduced oxygen contents. Although carbon lowers the melt density, the effect is modest at high pressures. Hence, it is likely that silicate melt above and below the mantle transition zone, and atop the core-mantle boundary could efficiently sequester significant amounts of carbon without being gravitationally unstable.

Extremely long transition phase of thermal convection in the mantle of massive super-Earths

Adiabatic compression is a key factor that exerts control over thermal convection in the compressible solid mantle of super-Earths. To discuss the effects of adiabatic compression, we present a numerical model of transient convection in the cooling mantle of a super-Earth that is ten times larger in size than the Earth. The calculations started with the shallow mantle that was hotter than expected by the extrapolation from the deep mantle conditions. This type of initial thermal state of the mantle is expected to naturally occur in real super-Earths due to heating by giant impacts at the time of their formation. With our initial setup conditions, the convection temporarily occurs as a layered convection for the first several to ten billion years of the calculation and then changes its style into a whole layer convection. The long duration of the transient stage suggests that mantle convection currently occurs as a temporal layered convection in many of the super-Earths. A temporal layered convection, if it occurs, can exert control over the tectonic activities of super-Earths. Future studies should clarify how internal heating and complicated rheological properties of mantle materials including their pressure dependence affect the duration of the temporal layered convection.Graphical abstract.

Diamond formation in the deep lower mantle: a high-pressure reaction of MgCO3 and SiO2

Diamond is an evidence for carbon existing in the deep Earth. Some diamonds are considered to have originated at various depth ranges from the mantle transition zone to the lower mantle. These diamonds are expected to carry significant information about the deep Earth. Here, we determined the phase relations in the MgCO3-SiO2 system up to 152 GPa and 3,100 K using a double sided laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. MgCO3 transforms from magnesite to the high-pressure polymorph of MgCO3, phase II, above 80 GPa. A reaction between MgCO3 phase II and SiO2 (CaCl2-type SiO2 or seifertite) to form diamond and MgSiO3 (bridgmanite or post-perovsktite) was identified in the deep lower mantle conditions. These observations suggested that the reaction of the MgCO3 phase II with SiO2 causes formation of super-deep diamond in cold slabs descending into the deep lower mantle.

Solid-liquid density and spin crossovers in (Mg, Fe)O system at deep mantle conditions.

The low/ultralow-velocity zones in the Earth’s mantle can be explained by the presence of partial melting, critically depending on density contrast between the melt and surrounding solid mantle. Here, first-principles molecular dynamics simulations of (Mg, Fe) O ferropericlase in the solid and liquid states show that their densities increasingly approach each other as pressure increases. The isochemical density difference between them diminishes from 0.78 (±0.7) g/cm3 at zero pressure (3000 K) to 0.16 (±0.04) g/cm3 at 135 GPa (4000 K) for pure and alloyed compositions containing up to 25% iron. The simulations also predict a high-spin to low-spin transition of iron in the liquid ferropericlase gradually occurring over a pressure interval centered at 55 GPa (4000 K) accompanied by a density increase of 0.14 (±0.02) g/cm3. Temperature tends to widen the transition to higher pressure. The estimated iron partition coefficient between the solid and liquid ferropericlase varies from 0.3 to 0.6 over the pressure range of 23 to 135 GPa. Based on these results, an excess of as low as 5% iron dissolved in the liquid could cause the solid-liquid density crossover at conditions of the lowermost mantle.

Quantitative analysis of hydrogen sites and occupancy in deep mantle hydrous wadsleyite using single crystal neutron diffraction.

Evidence from seismological and mineralogical studies increasingly indicates that water from the oceans has been transported to the deep earth to form water-bearing dense mantle minerals. Wadsleyite [(Mg, Fe2+)2SiO4] has been identified as one of the most important host minerals incorporating this type of water, which is capable of storing the entire mass of the oceans as a hidden reservoir. To understand the effects of such water on the physical properties and chemical evolution of Earth’s interior, it is essential to determine where in the crystal structure the hydration occurs and which chemical bonds are altered and weakened after hydration. Here, we conduct a neutron time-of-flight single-crystal Laue diffraction study on hydrous wadsleyite. Single crystals were grown under pressure to a size suitable for the experiment and with physical qualities representative of wet, deep mantle conditions. The results of this neutron single crystal diffraction study unambiguously demonstrate the method of hydrogen incorporation into the wadsleyite, which is qualitatively different from that of its denser polymorph, ringwoodite, in the wet mantle. The difference is a vital clue towards understanding why these dense mantle minerals show distinctly different softening behaviours after hydration.

Iron spin state and site distribution in FeAlO3-bearing bridgmanite

DFT at the GGA, GGA+U and hybrid functional levels were used to investigate thousands of different Al and Fe3+ configurations of MgSiO3–FeAlO3 (MS–FA) and MgSiO3–FeAlO3–Al2O3 bridgmanite at deep mantle conditions. Comparison of the different functionals and atomic charge analysis suggests that GGA, frequently used to explain high to low spin transitions observed in several Mössbauer and X-ray emission spectroscopy experiments, is hampered by spurious self-interaction errors in the exchange-correlation energy. Configurational Boltzmann averaging shows that the B site is thermally inaccessible to Fe3+ at the GGA+U and hybrid levels, and we find no evidence for a spin-pairing transition in fully (thermodynamically) equilibrated samples of bridgmanite, even at the lowermost mantle conditions. The comparison of the cation radii of Fe3+ and Mg supports a spin transition accompanied by a site exchange, but the flexibility of FeO bonds to locally adapt promotes the incorporation of iron in the irregularly coordinated A-site. The concept of ionic radii is therefore unsuitable for analysis of spin state and site exchange in bridgmanite at these conditions. Consistent with previous computational work and experimental studies with glass and gel as starting material, we find that ferric iron kinetically trapped at the B site undergoes a spin transition under lowermost mantle conditions. In bridgmanite with mole fraction of Fe3+>Al a charge-balancing amount of low spin Fe3+ will be thermodynamically stable at the B site, but because bridgmanite in peridotitic and basaltic lithologies mostly has Al/Fetotal above unity, FA with high spin Fe3+ in the A-site will be the dominant iron component. The lack of a Fe3+ spin transition in the FA-component has important implications for bridgmanite–ferropericlase partitioning of iron and magnesium and the mineral physics of the lowermost mantle.

The thermal equation of state of (Mg, Fe)SiO3bridgmanite (perovskite) and implications for lower mantle structures

AbstractThe high‐pressure/high‐temperature equation of state (EOS) of synthetic 13% Fe‐bearing bridgmanite (Mg silicate perovskite) is measured using powder X‐ray diffraction in a laser‐heated diamond anvil cell with a quasi‐hydrostatic neon pressure medium. We compare these results, which are consistent with previous 300 K sound speed and compression studies, with a reanalysis of Fe‐free Mg end‐member data from Tange et al. (2012) to determine the effect of iron on bridgmanite's thermoelastic properties. EOS parameters are incorporated into an ideal lattice mixing model to probe the behavior of bridgmanite at deep mantle conditions. With this model, a nearly pure bridgmanite mantle composition is shown to be inconsistent with density and compressibility profiles of the lower mantle. We also explore the buoyant stability of bridgmanite over a range of temperatures and compositions expected for Large Low‐Shear Velocity Provinces, concluding that bridgmanite‐dominated thermochemical piles are more likely to be passive dense layers externally supported by convection, rather than internally supported metastable domes. The metastable dome scenario is estimated to have a relative likelihood of only 4–7%, given the narrow range of compositions and temperatures consistent with seismic constraints. If buoyantly supported, such structures could not have remained stable with greater thermal contrast early in Earth's history, ruling out formation scenarios involving a large concentration of heat producing elements.

Coordinated Hard Sphere Mixture (CHaSM): A simplified model for oxide and silicate melts at mantle pressures and temperatures

We develop a new model to understand and predict the behavior of oxide and silicate melts at extreme temperatures and pressures, including deep mantle conditions like those in the early Earth magma ocean. The Coordinated Hard Sphere Mixture (CHaSM) is based on an extension of the hard sphere mixture model, accounting for the range of coordination states available to each cation in the liquid. By utilizing approximate analytic expressions for the hard sphere model, this method is capable of predicting complex liquid structure and thermodynamics while remaining computationally efficient, requiring only minutes of calculation time on standard desktop computers. This modeling framework is applied to the MgO system, where model parameters are trained on a collection of crystal polymorphs, producing realistic predictions of coordination evolution and the equation of state of MgO melt over a wide range of pressures and temperatures. We find that the typical coordination number of the Mg cation evolves continuously upward from 5.25 at 0GPa to 8.5 at 250GPa. The results produced by CHaSM are evaluated by comparison with predictions from published first-principles molecular dynamics calculations, indicating that CHaSM is accurately capturing the dominant physics controlling the behavior of oxide melts at high pressure. Finally, we present a simple quantitative model to explain the universality of the increasing Grüneisen parameter trend for liquids, which directly reflects their progressive evolution toward more compact solid-like structures upon compression. This general behavior is opposite that of solid materials, and produces steep adiabatic thermal profiles for silicate melts, thus playing a crucial role in magma ocean evolution.

Structures and stability of calcium and magnesium carbonates at mantle pressures

Ab initio random structure searching (AIRSS) and density functional theory methods are used to predict structures of calcium and magnesium carbonate $({\mathrm{CaCO}}_{3}$ and ${\mathrm{MgCO}}_{3})$ at high pressures. We find a previously unknown ${\mathrm{CaCO}}_{3}$ structure which is more stable than the aragonite and ``post aragonite'' phases in the range 32--48 GPa. At pressures from 76 GPa to well over 100 GPa the most stable phase is a previously unknown ${\mathrm{CaCO}}_{3}$ structure of the pyroxene type with fourfold coordinated carbon atoms. We also predict a stable structure of ${\mathrm{MgCO}}_{3}$ in the range 85--101 GPa. Our results lead to a revision of the phase diagram of ${\mathrm{CaCO}}_{3}$ over more than half the pressure range encountered within the Earth's mantle, and smaller changes to the phase diagram of ${\mathrm{MgCO}}_{3}$. We predict ${\mathrm{CaCO}}_{3}$ to be more stable than ${\mathrm{MgCO}}_{3}$ in the Earth's mantle above 100 GPa, and that ${\mathrm{CO}}_{2}$ is not a thermodynamically stable compound under deep mantle conditions. Our results have significant implications for understanding the Earth's deep carbon cycle.

High-pressure orthorhombic ferromagnesite as a potential deep-mantle carbon carrier.

Knowledge of the physical and chemical properties of candidate deep-carbon carriers such as ferromagnesite [(Mg,Fe)CO3] at high pressure and temperature of the deep mantle is necessary for our understanding of deep-carbon storage as well as the global carbon cycle of the planet. Previous studies have reported very different scenarios for the (Mg,Fe)CO3 system at deep-mantle conditions including the chemical dissociation to (Mg,Fe)O+CO2, the occurrence of the tetrahedrally-coordinated carbonates based on CO4 structural units, and various high-pressure phase transitions. Here we have studied the phase stability and compressional behavior of (Mg,Fe)CO3 carbonates up to relevant lower-mantle conditions of approximately 120 GPa and 2400 K. Our experimental results show that the rhombohedral siderite (Phase I) transforms to an orthorhombic phase (Phase II with Pmm2 space group) at approximately 50 GPa and 1400 K. The structural transition is likely driven by the spin transition of iron accompanied by a volume collapse in the Fe-rich (Mg,Fe)CO3 phases; the spin transition stabilizes the high-pressure phase II at much lower pressure conditions than its Mg-rich counterpart. It is conceivable that the low-spin ferromagnesite phase II becomes a major deep-carbon carrier at the deeper parts of the lower mantle below 1900 km in depth.

Stability of hydrous phase H MgSiO4H2 under lower mantle conditions

AbstractWe report the stability field of a new high‐pressure hydrous phase, phase H MgSiO4H2, and its implications for water transport into the deep lower mantle. We observed the existence of hydrous phase H at pressures around 50 GPa, and this phase was stable up to 60 GPa. Our results, together with those of previous works, indicate that pure phase H MgSiO4H2 has a very narrow stability field in the pressure range 35 < P < 60 GPa, equivalent to the uppermost part of the lower mantle. The stability field expands significantly toward higher pressures and temperatures on dissolution of the hydrous AlOOH component. The hydrous phase H‐phase δ solid solution (aluminous phase H), (MgSi,Al2)O4H2, is potentially the most important hydrous phase present under the deep lower mantle conditions.

Rheology of fine‐grained forsterite aggregate at deep upper mantle conditions

AbstractHigh‐pressure and high‐temperature deformation experiments on fine‐grained synthetic dunite (forsterite aggregate) were conducted to determine the dominant deformation mechanism in the deep upper mantle. The sintered starting material has 90% forsterite, 10% enstatite, and an average grain size of ~1 µm. Deformation experiments were performed using a deformation‐DIA apparatus at pressures of 3.03–5.36 GPa, temperatures of 1473–1573 K, and uniaxial strain rates of 0.91 × 10−5 to 18.6 × 10−5 s−1 at dry circumstances <50 H/106Si. The steady state flow stress was determined at each deformation condition. Derived stress‐strain rate data is analyzed together with that reported from similar but low‐pressure deformation experiments using flow law equations for diffusion creep (stress exponent of n = 1, grain‐size exponent of p = 2) and for dislocation‐accommodated grain‐boundary sliding (GBS‐disl, n = 3, p = 1). The activation volume for diffusion creep (V*dif) and for GBS‐disl (V*GBS) of dunite is determined to be 8.2 ± 0.9 and 7.5 ± 1.0 cm3/mol, respectively. Calculations based on these results suggest that both diffusion creep and dislocation creep play an important role for material flow at typical deformation conditions in the Earth's asthenospheric upper mantle whereas the contribution of GBS‐disl is very limited, and dislocation creep is the dominant deformation mechanism during the deformation of olivine in sheared peridotite xenolith. Though these conclusions are not definitive, these are the first results on potential deformation mechanisms of forsterite aggregate based on extrapolation in the pressure, temperature, stress, and grain‐size space.

Structural change in molten basalt at deep mantle conditions

Silicate liquids play a key part at all stages of deep Earth evolution, ranging from core and crust formation billions of years ago to present-day volcanic activity. Quantitative models of these processes require knowledge of the structural changes and compression mechanisms that take place in liquid silicates at the high pressures and temperatures in the Earth's interior. However, obtaining such knowledge has long been impeded by the challenging nature of the experiments. In recent years, structural and density information for silica glass was obtained at record pressures of up to 100 GPa (ref. 1), a major step towards obtaining data on the molten state. Here we report the structure of molten basalt up to 60 GPa by means of in situ X-ray diffraction. The coordination of silicon increases from four under ambient conditions to six at 35 GPa, similar to what has been reported in silica glass. The compressibility of the melt after the completion of the coordination change is lower than at lower pressure, implying that only a high-order equation of state can accurately describe the density evolution of silicate melts over the pressure range of the whole mantle. The transition pressure coincides with a marked change in the pressure-evolution of nickel partitioning between molten iron and molten silicates, indicating that melt compressibility controls siderophile-element partitioning.

P–V–T equation of state of siderite to 33 GPa and 1673 K

Pressure–volume–temperature relations have been measured to 33GPa and 1673K for natural siderite (Fe0.95Mn0.05CO3) using synchrotron X-ray diffraction with a multianvil apparatus at the ‘SPring-8’ facility. A least-squares fit of the room-temperature compression data to a third-order Birch–Murnaghan equation of state (EOS) yielded K0=120±1GPa and K′=3.57±0.09, with fixed V0=293.4±0.1Å3. Further analysis of the high-temperature compression data yielded the temperature derivative of the bulk modulus (∂KT/∂T)P=−0.015±0.001GPa/K and zero-pressure thermal expansion α=a0+a1T with a0=3.57(9)×10−5K−1 and a1=0.06(14)×10−8K−2. The analysis of axial compressibility indicates that the c-axis is more compressible (KTc=59±1GPa at K′=2.7±0.1) than the a-axis (KTa=166±2GPa at K′=14.0±0.8). The present thermal EOS enables accurate calculation the density and thermodynamic properties of siderite to the deep mantle conditions.

Electronic structure of iron in magnesium silicate glasses at high pressure

A recent study attributed the source of an iron partitioning change between silicate melt and minerals at deep mantle conditions to a high‐spin to low‐spin change in iron, which was found in a Fe‐diluted Mg‐silicate glass at a similar pressure. We conducted X‐ray emission spectroscopy and nuclear forward scattering on iron‐rich Mg‐silicate glasses at high pressure and 300 K in the diamond‐anvil cell: Al‐free glass up to 135 GPa and Al‐bearing glass up to 93 GPa. In both glasses, the spin moment decreases gradually from 1 bar and does not reach a complete low‐spin state even at the peak pressures of this study. The gradual change may be due to the existence of diverse coordination environments for iron in the glasses and continuous structural adjustment of the disordered system with pressure. If the result can be extrapolated to iron in mantle melts, the small, gradual changes in the spin state of iron may not be the dominant factor explaining the reported sudden change in the partitioning behavior of iron between silicate melt and minerals at lower‐mantle pressures.

Thermal conductivity of MgO, MgSiO3 perovskite and post-perovskite in the Earth's deep mantle

We report lattice thermal conductivities of MgO and MgSiO3 in the perovskite and post-perovskite structures at conditions of the Earth's lower mantle, obtained from equilibrium molecular dynamics simulations. Using an advanced ionic interaction potential, the full conductivity tensor was calculated by means of the Green–Kubo method, and the conductivity of MgSiO3 post-perovskite was found to be significantly anisotropic. The thermal conductivities of all three phases were parameterized as a function of density and temperature. Assuming a Fe-free lower-mantle composition with mole fractions xMgSiO3=0.66 and xMgO=0.34, the conductivity of the two-phase aggregate was calculated along a model geotherm. It was found to vary considerably with depth, rising from 9.5W/(mK) at the top of the lower mantle to 20.5W/(mK) at the top of the thermal boundary layer above the core–mantle boundary. Extrapolation of experimental data suggests that at deep-mantle conditions, the presence of a realistic amount of iron impurities lowers the thermal conductivity of the aggregate by about 50% (Manthilake et al., 2011a). From this result and our thermal conductivity model, we estimate the heat flux across the core–mantle boundary to be 10.8TW for a Fe-bearing MgO/MgSiO3 perovskite aggregate and 10.6TW for a Fe-bearing MgO/MgSiO3 post-perovskite aggregate.

Solid–liquid iron partitioning in Earth’s deep mantle

Melting processes in the deep mantle have important implications for the origin of the deep-derived plumes believed to feed hotspot volcanoes such as those in Hawaii. They also provide insight into how the mantle has evolved, geochemically and dynamically, since the formation of Earth. Melt production in the shallow mantle is quite well understood, but deeper melting near the core-mantle boundary remains controversial. Modelling the dynamic behaviour of deep, partially molten mantle requires knowledge of the density contrast between solid and melt fractions. Although both positive and negative melt buoyancies can produce major chemical segregation between different geochemical reservoirs, each type of buoyancy yields drastically different geodynamical models. Ascent or descent of liquids in a partially molten deep mantle should contribute to surface volcanism or production of a deep magma ocean, respectively. We investigated phase relations in a partially molten chondritic-type material under deep-mantle conditions. Here we show that the iron partition coefficient between aluminium-bearing (Mg,Fe)SiO(3) perovskite and liquid is between 0.45 and 0.6, so iron is not as incompatible with deep-mantle minerals as has been reported previously. Calculated solid and melt density contrasts suggest that melt generated at the core-mantle boundary should be buoyant, and hence should segregate upwards. In the framework of the magma oceans induced by large meteoritic impacts on early Earth, our results imply that the magma crystallization should push the liquids towards the surface and form a deep solid residue depleted in incompatible elements.

Dolomite III: A new candidate lower mantle carbonate

Dolomite is a major constituent of subducted carbonates; therefore evaluation of its phase stability and equation of state at high pressures and temperatures is important for understanding the deep Earth carbon cycle. X-ray diffraction experiments in the diamond anvil cell show that Ca{sub 0.988}Mg{sub 0.918}Fe{sub 0.078}Mn{sub 0.016}(CO{sub 3}){sub 2} dolomite transforms to dolomite-II at {approx}17 GPa and 300 K and then upon laser-heating transforms to a new monoclinic phase (dolomite-III), that is observed between 36 and 83 GPa. Both high-pressure polymorphs are stable up to 1500 K, indicating that addition of minor Fe stabilizes dolomite to Earth's deep-mantle conditions.

Spin crossover and iron-rich silicate melt in the Earth’s deep mantle

A melt has greater volume than a silicate solid of the same composition. But this difference diminishes at high pressure, and the possibility that a melt sufficiently enriched in the heavy element iron might then become more dense than solids at the pressures in the interior of the Earth (and other terrestrial bodies) has long been a source of considerable speculation. The occurrence of such dense silicate melts in the Earth's lowermost mantle would carry important consequences for its physical and chemical evolution and could provide a unifying model for explaining a variety of observed features in the core-mantle boundary region. Recent theoretical calculations combined with estimates of iron partitioning between (Mg,Fe)SiO(3) perovskite and melt at shallower mantle conditions suggest that melt is more dense than solids at pressures in the Earth's deepest mantle, consistent with analysis of shockwave experiments. Here we extend measurements of iron partitioning over the entire mantle pressure range, and find a precipitous change at pressures greater than ∼76 GPa, resulting in strong iron enrichment in melts. Additional X-ray emission spectroscopy measurements on (Mg(0.95)Fe(0.05))SiO(3) glass indicate a spin collapse around 70 GPa, suggesting that the observed change in iron partitioning could be explained by a spin crossover of iron (from high-spin to low-spin) in silicate melt. These results imply that (Mg,Fe)SiO(3) liquid becomes more dense than coexisting solid at ∼1,800 km depth in the lower mantle. Soon after the Earth's formation, the heat dissipated by accretion and internal differentiation could have produced a dense melt layer up to ∼1,000 km in thickness underneath the solid mantle. We also infer that (Mg,Fe)SiO(3) perovskite is on the liquidus at deep mantle conditions, and predict that fractional crystallization of dense magma would have evolved towards an iron-rich and silicon-poor composition, consistent with seismic inferences of structures in the core-mantle boundary region.